The present study describes the room-temperature cathodeluminescence (CL) and temperature-dependent photoluminescence (PL) properties of p-type lithium (Li)-doped zinc oxide (ZnO) nanowires (NWs) grown by hydrothermal doping and post-annealing processes. A ZnO thin film was used as a seed layer in NW growth. The emission wavelengths and intensities of undoped ZnO NWs and p-type Li-doped ZnO NWs were analyzed for comparison. CL and PL observations of post-annealed p-type Li-doped ZnO NWs clearly exhibited a dominant sharp band-edge emission. Finally, a n-type ZnO thin film/p-type annealed Li-doped ZnO NW homojunction diode was prepared to confirm the p-type conduction of annealed Li-doped ZnO NWs as well as the structural properties measured by transmission electron microscopy.